Berlin 2014 – scientific programme

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MO: Fachverband Molekülphysik

MO 18: Theory 3: Quantum Chemistry

MO 18.3: Talk

Thursday, March 20, 2014, 14:30–14:45, BEBEL SR144

Exact factorization of the electron-nuclear wave function: Applications — •Federica Agostini — Max Planck Institute of Microstructure Physics, Halle, Germany

The exact factorization [1] of the molecular wave function offers a new perspective on the correlated dynamics of electrons and nuclei. In particular, the Hamiltonian generating the nuclear evolution contains time dependent vector and scalar potentials. These potentials are uniquely defined, up to within a gauge transformation, and govern nuclear dynamics, yielding the nuclear wave function. They represent the exact electronic effect on the nuclei.

This reformulation of the time dependent Schroedinger equation is the starting point for the development of approximations, consisting in the classical treatment of only the nuclear degrees of freedom. With this objective in mind, we investigate the properties of the potentials in a model for proton coupled electron transfer. The exact solution of the full quantum mechanical problem gives access to the scalar potential [2,3], in a gauge where the vector potential is zero. We study the features of the potential and we test the performance of the classical approximation, given that the exact effect of the electrons on the nuclei is known.

[1] A. Abedi, N.T. Maitra and E.K.U. Gross, Phys. Rev. Lett. 105 (2010); J. Chem. Phys. 137 (2012) [2] A. Abedi, F. Agostini,Y. Suzuki and E.K.U. Gross, Phys. Rev. Lett. 110 (2013) [3] F. Agostini, A. Abedi, Y. Suzuki and E.K.U. Gross, Mol. Phys. 111 (2013)